The use of olefin polymerization catalysts based on bis .eta..sup.5 cyclopentadienyl complexes of transition metals (metallocenes) and related mono .eta..sup.5 cyclopentadienyl complexes (which are also often referred to as metallocenes) in olefin polymerization is now widely known. These complexes may be activated by the aluminum alkyls and/or aluminum alkyl halides which are conventionally used with so-called "Ziegler Natta" polymerization catalysts, although the use of such conventional activators usually does not provide a highly active catalyst.
Professors Kaminsky and Sinn discovered that alumoxanes are excellent activators for zirconocenes in homogeneous polymerizations. However, the catalyst systems reported by Kaminsky and Sinn typically contained a very large excess of the alumoxane (as much as 10,000/1 excess of the aluminum to the transition metal on a molar basis).
It has not been found to be commercially practical to utilize such a large excess of aluminum for supported catalysts. Most notably, it is difficult to effectively support large quantities of the alumoxane. The lower amount of supported aluminoxane used in the supported form of these catalysts has the effect of increasing the aluminum/transition metal ("Al/M") ratios of such catalysts. Simply put, the metal concentration would need to approach impractically low levels to maintain the Al/M ratio, given the limited amount of alumoxane which may be supported. Welborn and Turner disclose several forms of supported Kaminsky/Sinn catalysts which have low Al/M ratios (see, for example, U.S. Pat. No. 4,897,455 and U.S. Pat. No. 5,077,255).
Hlatky and Turner subsequently made the very elegant invention relating to the use of so-called "substantially non-coordinating anions" to activate bis-Cp metallocenes (as disclosed in U.S. Pat. No. 5,153,157 and U.S. Pat. No. 5,198,401).
The present invention relates to a catalyst component which contains an organometallic complex of a group 4 metal having a cyclopentadienyl-type ligand and a phosphinimine ligand ("phosphinimine complex").
Literature references describing similar phosphinimine complexes include:
Cyclopentadienyl Titanium Complexes with aryldiasenido or phosphiniminato-Ligands by J. R. Dilworth, Journal of Organometallic Chemistry, 159 (1978) 47-52; PA1 Syntheses und Reaktionen von (.eta..sup.5 -Pentamethylcyclopentadienyl)-und (.eta..sup.5 Ethyltetramethylcyclopentadienyl)titantrifluorid by S. Manshoeh et al, Chem. Ber., 1993 136, 913-919; PA1 Neue Komplexe des Titans mit silylierten Aminoiminophosphoran - und Sulfodiimidliganden by R. Hasselbring et al, Zeitschrift fur anorganische und allgemeine Chemie, 619 (1993) 1543-1550; PA1 Phosphaniminato-Komplese des Titans, Syntheses und Kristallstrukturen von CpTiCl.sub.2 (NPMe.sub.3), [TiCl.sub.3 (NPMe.sub.3)].sub.2,Ti.sub.2 Cl.sub.5 (NPMe.sub.2 Ph).sub.3 und [Ti.sub.3 Cl.sub.6 (NPMe.sub.3).sub.5 ][BPh] by T. Rubenstahl et al, Zeitschrift fur anorganische und allgemeine Chemie, 620 (1994) 1741-1749; and PA1 Syntheses and reactivity of Aminobis(diorganylamino)phosphanes by G. Shick et al, Chem. Ber., 1996,129,911-917. PA1 (a) an organometallic complex comprising PA1 (b) a particulate support. PA1 B) Cp is a cyclopentadienyl-type ligand which is unsubstituted or substituted by up to five substituents independently selected from the group consisting of C.sub.1-10 hydrocarbyl radicals with the proviso that two hydrocarbyl radicals taken together may form a ring, wherein said substituents or ring are unsubstituted or further substituted by substituents selected from the group consisting of: PA1 a) a halogen atom, PA1 b) a C.sub.1-8 alkyl radical, PA1 c) a C.sub.1-8 alkoxy radical, PA1 d) a C.sub.6-10 aryl or aryloxy radical, PA1 e) an amido radical which is unsubstituted or substituted by up to two C.sub.1-8 alkyl radicals, PA1 f) a phosphido radical which is unsubstituted or substituted by up to two C.sub.1-8 alkyl radicals, PA1 g) a silyl radical of the formula --Si--(R.sup.2).sub.3 wherein each R.sup.2 is independently selected from the group consisting of hydrogen, a C.sub.1-8 alkyl or alkoxy radical, C.sub.6-10 aryl or aryloxy radicals, PA1 h) a germanyl radical of the formula Ge--(R.sup.21).sub.3 wherein each R.sup.21 is independently selected from the group consisting of hydrogen, a C.sub.1-8 alkyl or alkoxy radical, C.sub.6-10 aryl or aryloxy radicals; PA1 C) each R.sup.1 is independently selected from the group consisting of: PA1 i) a hydrogen atom, PA1 j) a halogen atom, PA1 k) C.sub.1-10 hydrocarbyl radicals which are unsubstituted by or further substituted by a halogen atom, a C.sub.1-8 alkyl radical, C.sub.1-8 alkoxy radical, a C.sub.6-10 aryl or aryloxy radical, PA1 l) a silyl radical of the formula --Si--(R.sup.22).sub.3 wherein each R.sup.22 is independently selected from the group consisting of hydrogen, a C.sub.1-8 alkyl or alkoxy radical, C.sub.6-10 aryl or aryloxy radicals, PA1 m) a germanyl radical of the formula Ge--(R.sup.23).sub.3 wherein each R.sup.23 is independently selected from the group consisting of hydrogen, a C.sub.1-8 alkyl or alkoxy radical, C.sub.6-10 aryl or aryloxy radicals, PA1 n) a halogen atom, PA1 o) a C.sub.1-8 alkyl radical, PA1 p) a C.sub.1-8 alkoxy radical, PA1 q) a C.sub.6-10 aryl or aryloxy radical, PA1 r) a silyl radical of the formula --Si--(R.sup.24).sub.3 wherein each R.sup.24 is independently selected from the group consisting of hydrogen, a C.sub.1-8 alkyl or alkoxy radical, C.sub.6-10 aryl or aryloxy radicals, PA1 s) a germanyl radical of the formula Ge--(R.sup.25).sub.3 wherein each R.sup.25 is independently selected from the group consisting of hydrogen, a C.sub.1-8 alkyl or alkoxy radical, C.sub.6-10 aryl or aryloxy radicals; PA1 D) each L.sup.1 is independently selected from the group consisting of: PA1 t) a hydrogen atom, PA1 u) a halogen atom, PA1 v) a C.sub.1-10 hydrocarbyl radical, PA1 w) a C.sub.1-10 alkoxy radical, PA1 x) a C.sub.6-10 aryl oxide radical, PA1 y) a halogen atom, PA1 z) a C.sub.1-8 alkyl radical, PA1 aa) a C.sub.1-8 alkoxy radical, PA1 bb) a C.sub.6-10 aryl or aryloxy radical, PA1 cc) an amido radical which is unsubstituted or substituted by up to two C.sub.1-8 alkyl radicals, PA1 dd) a phosphido radical which is unsubstituted or substituted by up to two C.sub.1-8 alkyl radicals, PA1 Preferred Polymerization Temperatures: about 75.degree. C. to about 115.degree. C. (with the lower temperatures being preferred for lower melting copolymers--especially those having densities of less than 0.915 g/cc--and the higher temperatures being preferred for higher density copolymers and homopolymers); and PA1 Pressure: up to about 1000 psi (with a preferred range of from about 100 to 350 psi for olefin polymerization). PA1 (i) an aluminoxane; and PA1 (ii) a combination of an alkylating activator and an activator capable of ionizing the group 4 metal complex. PA1 (i) compounds of the formula [R.sup.5 ].sup.+ [B(R.sup.7).sub.4 ].sup.- wherein B is a boron atom, R.sup.5 is a cyclic C.sub.5-7 aromatic cation or a triphenyl methyl cation and each R.sup.7 is independently selected from the group consisting of phenyl radicals which are unsubstituted or substituted with from 3 to 5 substituents selected from the group consisting of a fluorine atom, a C.sub.1-4 alkyl or alkoxy radical which is unsubstituted or substituted by a fluorine atom; and a silyl radical of the formula --Si--(R.sup.9).sub.3 ; wherein each R.sup.9 is independently selected from the group consisting of a hydrogen atom and a C.sub.1-4 alkyl radical; and PA1 (ii) compounds of the formula [(R.sup.8).sub.t ZH].sup.+ [B(R.sup.7).sub.4 ].sup.- wherein B is a boron atom, H is a hydrogen atom, Z is a nitrogen atom or phosphorus atom, t is 2 or 3 and R.sup.8 is selected from the group consisting of C.sub.1-8 alkyl radicals, a phenyl radical which is unsubstituted or substituted by up to three C.sub.1-4 alkyl radicals, or one R.sup.8 taken together with the nitrogen atom may form an anilinium radical and R.sup.7 is as defined above; and PA1 (iii) compounds of the formula B(R.sup.7).sub.3 wherein R.sup.7 is as defined above. PA1 triethylammonium tetra(phenyl)boron, PA1 tripropylammonium tetra(phenyl)boron, PA1 tri(n-butyl)ammonium tetra(phenyl)boron, PA1 trimethylammonium tetra(p-tolyl)boron, PA1 trimethylammonium tetra(o-tolyl)boron, PA1 tributylammonium tetra(pentafluorophenyl)boron, PA1 tripropylammonium tetra (o,p-dimethylphenyl)boron, PA1 tributylammonium tetra(m,m-dimethylphenyl)boron, PA1 tributylammonium tetra(p-trifluoromethylphenyl)boron, PA1 tributylammonium tetra(pentafluorophenyl)boron, PA1 tri(n-butyl)ammonium tetra (o-tolyl)boron PA1 N,N-dimethylanilinium tetra(phenyl)boron, PA1 N,N-diethylanilinium tetra(phenyl)boron, PA1 N,N-diethylanilinium tetra(phenyl)n-butylboron, PA1 N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron PA1 di-(isopropyl)ammonium tetra(pentafluorophenyl)boron, PA1 dicyclohexylammonium tetra (phenyl)boron PA1 triphenylphosphonium tetra)phenyl)boron, PA1 tri(methylphenyl)phosphonium tetra(phenyl)boron, PA1 tri(dimethylphenyl)phosphonium tetra(phenyl)boron, PA1 tropillium tetrakispentafluorophenyl borate, PA1 triphenylmethylium tetrakispentafluorophenyl borate, PA1 benzene (diazonium) tetrakispentafluorophenyl borate, PA1 tropillium phenyltris-pentafluorophenyl borate, PA1 triphenylmethylium phenyl-trispentafluorophenyl borate, PA1 benzene (diazonium) phenyltrispentafluorophenyl borate, PA1 tropillium tetrakis (2,3,5,6-tetrafluorophenyl) borate, PA1 triphenylmethylium tetrakis (2,3,5,6-tetrafluorophenyl) borate, PA1 benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) borate, PA1 tropillium tetrakis (3,4,5-trifluorophenyl) borate, PA1 benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) borate, PA1 tropillium tetrakis (1,2,2-trifluoroethenyl) borate, PA1 trophenylmethylium tetrakis (1,2,2-trifluoroethenyl ) borate, PA1 benzene (diazonium) tetrakis (1,2,2-trifluoroethenyl) borate, PA1 tropillium tetrakis (2,3,4,5-tetrafluorophenyl) borate, PA1 triphenylmethylium tetrakis (2,3,4,5-tetrafluorophenyl) borate, and PA1 benzene (diazonium) tetrakis (2,3,4,5-tetrafluorophenyl) borate. PA1 triphenylmethylium tetrakispentafluorophenyl borate ("[Ph.sub.3 C][B(C.sub.6 F.sub.5).sub.4 ]"); and PA1 trispentafluorophenyl boron. PA1 Technique 1: First deposit the group 4 OMC on the support (then support the activator); PA1 Technique 2: First deposit the activator on the support (then support the group 4 OMC); or PA1 Technique 3: Support a mixture (solution or slurry) of the group 4 OMC and the activator at the same time.
While the above art discloses some of the related complexes per se, and in one instance the complex in conjunction with an activator, the art does not disclose the polymerization of olefins, and in particular the polymerization of olefins using a supported form of the complex.
A poster presentation by J. C. Stewart and D. W. Stephan, Department of Chemistry and Biochemistry, The University of Windsor, at the IDW conference at McGill University in November 1996, discloses polymerization of ethylene using certain cyclopentadienyl-phosphinimine catalysts. The turnover in terms of grams of polyethylene/mmol/hr (e.g. productivity or activity) is several orders of magnitude below that obtained with the catalyst components of the present invention. The poster presentation does not disclose the use of the supported catalyst components of the present invention, or polymerization above room temperature, or productivity/activity results which approach commercial utility.
U.S. Pat. No. 5,625,016, issued Apr. 29, 1997, assigned to Exxon Chemical Patents Inc. discloses the polymerization of olefins and in particular the preparation of ethylene propylene rubbers or ethylene propylene diene monomer copolymers, in the presence of a catalyst system prepared from an unbridged group 4 metal, a bulky (substituted) monocyclopentadienyl ligand, a uninegative bulky group 15 ligand and two uninegative activation reactive ligands. The disclosure of the patent teaches the group 15 ligand is an amido ligand. The '016 patent does not teach or suggest the use of a phosphinimine ligand.